CN101042365A - Dissolved oxygen electrochemical sensor - Google Patents
Dissolved oxygen electrochemical sensor Download PDFInfo
- Publication number
- CN101042365A CN101042365A CN 200710067952 CN200710067952A CN101042365A CN 101042365 A CN101042365 A CN 101042365A CN 200710067952 CN200710067952 CN 200710067952 CN 200710067952 A CN200710067952 A CN 200710067952A CN 101042365 A CN101042365 A CN 101042365A
- Authority
- CN
- China
- Prior art keywords
- electrode
- interdigital
- gold
- dissolved oxygen
- electrochemical sensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000001301 oxygen Substances 0.000 title claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 48
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010931 gold Substances 0.000 claims abstract description 23
- 229910052737 gold Inorganic materials 0.000 claims abstract description 23
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims abstract description 4
- 239000003292 glue Substances 0.000 claims abstract description 4
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 9
- 229910000679 solder Inorganic materials 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 238000007650 screen-printing Methods 0.000 claims description 5
- 229920002120 photoresistant polymer Polymers 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000004044 response Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 241000370738 Chlorion Species 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 150000001455 metallic ions Chemical class 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229960002668 sodium chloride Drugs 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000003902 seawater pollution Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
This invention relates to one solution oxygen electrical and chemical sensor, which adopts wire network print technique to process cross gold electrode, cross Pt electrode, Ag/AgCl electrode and relative gold weld disc on A1203 ceramics base board; dripping the polyphenylacetylene liquid into cross gold electrode and cross electrode to remove rotation coating and lighted by ultraviolet light for 12 hours to fix sensor film with thickness for 200 to 300nm; coating the electrode except film and Ag/AgCl area by insulation glue to form insulation layer and the gold weld disc is coated with epoxy resin.
Description
Technical field
The present invention relates to a kind of electrochemical sensor, particularly a kind of dissolved oxygen electrochemical sensor.
Background technology
Because the fast development of industry causes pollution of waterhead serious day by day in recent years, the water source quality utmost point need be controlled.For the monitoring of water source quality, general all with the index of the dissolved oxygen DO in the water as the contaminated degree of water quality.If the dissolved oxygen DO height in the water represents that then this water quality is preferable; Otherwise,, represent that then the contaminated degree of this water quality is serious if the dissolved oxygen DO in the water is very low.
The measurement of oxygen in water mainly relies on dissolved oxygen sensor to finish.Dissolved oxygen sensor as far back as 1956 promptly by Clark[1] develop, its structure is the film coated electrode, liquid electrolyte is separated with tested solution with electrode, and for a long time electrode is contacted with liquid electrolyte, membraneous material selects for use oxygen to see through, the tygon that stops other material to pass through simultaneously.High oxygen permeability membraneous material commonly used also comprises [2] such as polytetrafluoroethylene PTFE, polyvinylchloride, silica gel.The action principle of dissolved oxygen sensor is: when oxygen is dissolved in the liquid electrolyte by the optional membrane, carry out electrochemical reaction with electrode surface, convert oxygen concentration to electric current or electric potential signal, signal is output after amplifier strengthens.
Dissolved oxygen sensor development so far, its technology is comparatively ripe, but still has some shortcomings to break through, the life problems of sensor when containing in the high-concentration chlorine ion solution.As when being used for the seawater dissolved oxygen DO and detecting, because the existence of chlorion, corrosion phenomenon can take place in sensor electrode behind the impressed voltage, so still there is not the desirable dissolved oxygen sensor that seawater pollution detects that can be used for so far.
Dissolved oxygen sensor mostly adopts the method [3,4,5] of macromolecule membrane coated electrodes such as cellulose acetate, PTFE and PVC at present; The shortcoming of cellulose acetate is to apply continuously voltage carries out in the dissolved oxygen sensing process, and this macromolecule membrane can be stopped up by the calcium ion in the water, causes sensor to have only 12 hours serviceable life; The dissolved oxygen sensor of PTFE film coated electrode preparation has only 24 hours serviceable life; Though the PVC film can reduce the calcium ion blocking problem, serviceable life was above 72 hours, but really have the restriction of PVC anti-storage time (shelf life), and when being used for that general river dissolved oxygen DO carried out actual measurement, the metallic ion deposition problems more will be a big hidden danger.In addition, corrosion reaction under wet environment, behind the impressed voltage, also can take place on the electrode in working electrode and be with a kind of metal material to electrode in the said method.
Summary of the invention
The object of the present invention is to provide a kind of dissolved oxygen electrochemical sensor, cover screen printing electrode with the polystyrene macromolecule membrane, working electrode with electrode is used different metal materials, can avoid chlorion in the solution, when metallic ion exists, cause the generation of electrode corrosion reaction behind the impressed voltage; Working electrode and electrode adopted interdigital electrode version can improve the response current rate of diffusion, strengthens the sensitivity of sensor.
A kind of dissolved oxygen electrochemical sensor comprises Al
2O
3Ceramic substrate, interdigital gold electrode 2 as working electrode, as interdigital Pt electrode 3 to electrode, Ag/AgCl electrode 4 as contrast electrode, and corresponding gold solder dish 5a, 5b, 5c, cover the sensing film 6 on interdigital gold electrode 2 and the interdigital Pt electrode 3, it is characterized in that: interdigital gold electrode 2, interdigital Pt electrode 3, Ag/AgCl electrode 4 and corresponding gold solder dish 5a, 5b, 5c are at Al with screen printing technique
2O
3Make on the ceramic substrate 1, sensing film 6 is dripped on interdigital gold electrode 2 and interdigital Pt electrode 3 with the photoresist spinner spin coating by polystyrene solution after UV-irradiation solidify to form in 12 hours, substrate is provided with one with insulating gel covered dielectric layer 7, gold solder dish 5a, the last coating of 5b, 5c epoxide resin AB glue; Sensing film 6 thickness are 200～300nm.
With prior art relatively, the present invention has following outstanding advantage: 1) the present invention covers the screen printing electrode surface with the polystyrene macromolecule membrane, electrode can be completely cut off with wet environment, when having chlorion or metallic ion in the solution, can avoid electrode corrosion behind the impressed voltage, reach 120 hours serviceable life; 2) working electrode with electrode is adopted different metal materials, further be reduced in the generation of wet environment bottom electrode corrosion reaction; 3) working electrode and electrode adopted interdigital electrode version improves the response current rate of diffusion, and sensor highly sensitive in 4～20ppm dissolved oxygen concentration scope, presents the good linear relation, and sensitivity is-6.05 μ A/ppm; 4) adopt at Al
2O
3Silk-screen electrode preparation dissolved oxygen electrochemical sensor on the ceramic substrate, microminiaturization is made simple, with low cost.
Description of drawings
Fig. 1 is the electrode structural chart of dissolved oxygen electrochemical sensor of the present invention.
Fig. 2 is the structural representation of dissolved oxygen electrochemical sensor of the present invention.
Fig. 3 is the current-responsive figure of this dissolved oxygen electrochemical sensor to dissolved oxygen concentration, and horizontal ordinate is a dissolved oxygen concentration, and ordinate is a response current intensity.
Embodiment
Embodiment 1:
A kind of dissolved oxygen electrochemical sensor, interdigital gold electrode 2, interdigital Pt electrode 3, Ag/AgCl electrode 4 and corresponding gold solder dish 5a, 5b, 5c are at Al with screen printing technique
2O
3Make on the ceramic substrate 1, the width of interdigital gold electrode 2 and interdigital Pt electrode 3, spacing are 0.5mm, the length of Ag/AgCl electrode 4 is 10mm, sensing film 6 is dripped on interdigital gold electrode 2 and interdigital Pt electrode 3 with the photoresist spinner spin coating after UV-irradiation solidify to form in 12 hours by polystyrene solution, and the area of sensing film 6 is 25.25mm
2, substrate is provided with one with insulating gel covered dielectric layer 7, gold solder dish 5a, the last coating of 5b, 5c epoxide resin AB glue; Sensing film 6 thickness are 200～300nm.As shown in Figure 1 and Figure 2.
At 1atm, temperature is under 25 ℃ the situation, be that dissolved oxygen content in 3% the sodium-chloride water solution is tested to mass concentration: at first in solution, fed nitrogen 25 minutes, compel the oxygen in the clean solution, feed a certain amount of oxygen then, oxygen concentration in the solution is 4ppm, use dissolved oxygen electrochemical sensor of the present invention, applying current potential is-0.6V (vs.Ag/AgCl), record corresponding response current value, like this process successively in the test solution dissolved oxygen concentration be respectively 6ppm, 8ppm, 10ppm, 12ppm, 14ppm, 16ppm, 18ppm, response current during 20ppm, obtain different dissolved oxygen concentration and sensor response current strength relationship, as shown in Figure 3.
In 4～20ppm dissolved oxygen concentration scope, present the good linear relation, transducer sensitivity is-6.05 μ A/ppm, is limited to 4ppm under detecting.
Use dissolved oxygen electrochemical sensor of the present invention, be continuously applied-0.6V (vs.Ag/AgCl) current potential and reach 120 hours, the dissolved oxygen content that to mass concentration is the 8ppm concentration in 3% the sodium-chloride water solution carries out follow-on test, response current remains on same stationary value, obviously corrosion does not take place in electrode, and sensor has the very long life-span.
List of references
1.Clark?L?C，Monitor?and?control?of?blood?and?tissue?oxygen?tension，Trans.Am.Soc.Artificial?Intern，1956，2：41～49
2.Hitchmam?M?L，Measurement?of?Dissolved?Oxygen，John?Wiley?&Sons，Inc.New?York，1978
3.Glasspool，W.V.and?Atkinson，J.K.，A?screen-printed?amperometric?dissolved?oxygensensor?utilising?an?immobilised?electrolyte?gel?and?membrane，Sensors?and?Actuators?B，1998，48：308～317
4.Atkinson?J?K，Glasspool?W?V，An?investigation?of?the?factors?influencing?stabilityin?continuously-powered?screen-printed?amperometric?dissolved?oxygen?sensors，Microelectronics?Internationa，2001，18(2)：26～30
5.Atkinson?J?K，Glasspool?W?V，An?evaluation?of?the?characteristics?of?membranematerials?suitable?for?the?batch?fabrication?of?dissolved?oxygen?sensors，MicroelectronicsInternationa，2003，20(2)：32～40。
Claims (2)
1. a dissolved oxygen electrochemical sensor comprises Al
2O
3Ceramic substrate (1), interdigital gold electrode (2) as working electrode, as interdigital Pt electrode (3) to electrode, as the Ag/AgCl electrode (4) of contrast electrode, and corresponding gold solder dish (5a, 5b, 5c), cover the sensing film (6) on interdigital gold electrode (2) and the interdigital Pt electrode (3), it is characterized in that: interdigital gold electrode (2), interdigital Pt electrode (3), Ag/AgCl electrode (4) and corresponding gold solder dish (5a, 5b is at Al with screen printing technique 5c)
2O
3Make on the ceramic substrate (1), sensing film (6) is dripped on interdigital gold electrode (2) and interdigital Pt electrode (3) with the photoresist spinner spin coating by polystyrene solution after UV-irradiation solidify to form in 12 hours, substrate is provided with one with insulating gel covered dielectric layer (7), gold solder dish (5a, 5b 5c) goes up coating epoxide resin AB glue.
2. dissolved oxygen electrochemical sensor according to claim 1 is characterized in that: sensing film (6) thickness is 200～300nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710067952 CN101042365A (en) | 2007-04-11 | 2007-04-11 | Dissolved oxygen electrochemical sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710067952 CN101042365A (en) | 2007-04-11 | 2007-04-11 | Dissolved oxygen electrochemical sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101042365A true CN101042365A (en) | 2007-09-26 |
Family
ID=38808036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710067952 Pending CN101042365A (en) | 2007-04-11 | 2007-04-11 | Dissolved oxygen electrochemical sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101042365A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101881749A (en) * | 2010-06-25 | 2010-11-10 | 浙江大学 | All-solid state dissolved oxygen sensor and preparation method thereof |
| CN102012392A (en) * | 2010-09-28 | 2011-04-13 | 浙江大学 | Screen printing electrode and application thereof |
| CN102272863A (en) * | 2010-03-17 | 2011-12-07 | 积水化学工业株式会社 | Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure |
| CN102645470A (en) * | 2012-03-31 | 2012-08-22 | 无锡百灵传感技术有限公司 | Preparation method of electrochemical sensor for dissolved oxygen detection |
| WO2018048362A1 (en) * | 2016-09-09 | 2018-03-15 | King Mongkut's University Of Technology Thonburi (Kmutt) | Process of production of interdigitated array of electrodes and derivatives by screen printing technique |
| CN114660136A (en) * | 2022-03-17 | 2022-06-24 | 浙江清华柔性电子技术研究院 | Electrochemical dissolved oxygen sensor and preparation method thereof |
| CN114858888A (en) * | 2022-04-02 | 2022-08-05 | 中山大学 | Method for measuring marine microorganism adhesion |
-
2007
- 2007-04-11 CN CN 200710067952 patent/CN101042365A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272863A (en) * | 2010-03-17 | 2011-12-07 | 积水化学工业株式会社 | Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure |
| CN101881749A (en) * | 2010-06-25 | 2010-11-10 | 浙江大学 | All-solid state dissolved oxygen sensor and preparation method thereof |
| CN102012392A (en) * | 2010-09-28 | 2011-04-13 | 浙江大学 | Screen printing electrode and application thereof |
| CN102645470A (en) * | 2012-03-31 | 2012-08-22 | 无锡百灵传感技术有限公司 | Preparation method of electrochemical sensor for dissolved oxygen detection |
| WO2018048362A1 (en) * | 2016-09-09 | 2018-03-15 | King Mongkut's University Of Technology Thonburi (Kmutt) | Process of production of interdigitated array of electrodes and derivatives by screen printing technique |
| CN114660136A (en) * | 2022-03-17 | 2022-06-24 | 浙江清华柔性电子技术研究院 | Electrochemical dissolved oxygen sensor and preparation method thereof |
| CN114858888A (en) * | 2022-04-02 | 2022-08-05 | 中山大学 | Method for measuring marine microorganism adhesion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Belmont et al. | Mercury-plated iridium-based microelectrode arrays for trace metals detection by voltammetry: optimum conditions and reliability | |
| CN101042365A (en) | Dissolved oxygen electrochemical sensor | |
| Zhang et al. | High sensitive on-site cadmium sensor based on AuNPs amalgam modified screen-printed carbon electrodes | |
| Quinton et al. | On-chip multi-electrochemical sensor array platform for simultaneous screening of nitric oxide and peroxynitrite | |
| Li et al. | A novel pH potentiometric sensor based on electrochemically synthesized polybisphenol A films at an ITO electrode | |
| Ping et al. | Determination of trace heavy metals in milk using an ionic liquid and bismuth oxide nanoparticles modified carbon paste electrode | |
| US10809223B2 (en) | Sensor | |
| TWI625522B (en) | Planar ammonia selective sensing electrode and manufacturing method thereof | |
| US20130270113A1 (en) | Electrochemical strip and manufacturing method thereof | |
| Kawde et al. | Cathodized gold nanoparticle‐modified graphite pencil electrode for non‐enzymatic sensitive voltammetric detection of glucose | |
| Batley | Electroanalytical techniques for the determination of heavy metals in seawater | |
| CN102262112A (en) | Alloy electrode electrochemical sensor for detecting trace heavy metals | |
| WO2014077017A1 (en) | Ozone water concentration measurement apparatus and ozone water concentration measurement method | |
| Ensafi et al. | Highly Sensitive Differential Pulse Voltammetric Determination of Cd, Zn and Pb Ions in Water Samples Using Stable Carbon‐Based Mercury Thin‐Film Electrode | |
| Schiavon et al. | Amperometric monitoring of sulphur dioxide in liquid and air samples of low conductivity by electrodes supported on ion-exchange membranes | |
| Baldo et al. | A study on the suitability of carbon disk microelectrodes for trace analysis of lead and copper by ASV | |
| Wu et al. | Construction of a selective non-enzymatic electrochemical sensor based on hollow nickel nanospheres/carbon dots–chitosan and molecularly imprinted polymer film for the detection of glucose | |
| Wang et al. | Mercury-coated carbon-foam composite electrodes for stripping analysis for trace metals | |
| JPH10513552A (en) | Electrochemical planar metal / metal oxide electrode | |
| Buffon et al. | Spectroscopic ellipsometry studies of an electrochemically synthesized molecularly imprinted polymer for the detection of an aviation biokerosene contaminant | |
| IE980529A1 (en) | The use of screen printed electrodes in the electrochemical analysis of electroactive species | |
| CN109254065A (en) | A kind of application of silica/poly- furfural modified electrode and preparation method thereof and detection lead cadmium ion | |
| Koster et al. | H2 quantification based on selective pre-concentration and oxidative stripping at Pd modified microelectrodes | |
| TWI775809B (en) | Electrode for electrochemical sensors | |
| Duong et al. | Facile synthesis of CuO/ITO film via the chronoamperometric electrodeposition for nonenzymatic glucose sensing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |